Salts of triazinic compounds with phosphorus oxyacids, and use of said compounds in self-extinguishing polymeric compositions

ABSTRACT

Salts of triazinic compounds with phosphorus oxyacids, having the general formula (I):    &lt;IMAGE&gt;  (I)  obtained by salifying oligomeric derivatives of 2,4,6-triamino-1,3,5-triazine with a phosphorus-containing acid. The compounds with general formula (I) find use in particular as flame-retardant additives.

The present invention relates to salts of triazinic compounds withphosphorus oxyacids.

More particularly, the present invention relates to salts of triaziniccompounds with phosphorus oxyacids, and to their use in the preparationof self-extinguishing polymeric compositions based on thermo-plasticpolymers, or on polymers with elastomeric properties, in particularolefinic polymers or copolymers.

In the art several solutions are known in order to reduce or eliminatethe combustibility of polymers. Some of such solutions are based on theuse of metal compounds, in particular of antimony, bismuth or arsenic,in combination with partially halogenated and thermally unstable organiccompounds, such as chlorinated paraffinic waxes.

Other solutions are based on the use of substances able to produceintumescence. The formulations of intumescent type are generallyconstituted by the polymer and at least three main additives: anessentially phosphorus-containing additive, the purpose of which is offorming, during combustion, a semisolid, impermeable glassy layeressentially constituted by polyphosphoric acid, and of activating theprocess leading to intumescence formation; a second additive whichcontains nitrogen and performs the function of foaming agent; and athird additive, which contains carbon and acts as a carbon donor inorder to form an insulating cellular carbonaceous layer (char) betweenthe polymer and the flame.

Examples of such a type of intumescent formulations are those reportedin the following patents: U.S. Pat. No. 3,810,862 (Phillips PetroleumCo.), based on melamine, pentaerythritol and ammonium polyphosphate;U.S. Pat. No. 4,727,102 (Vamp S.r.L.), based on melamine cyanurate, ahydroxyalkyl derivative of isocyanuric acid and ammonium polyphosphate;and published patent application WO 85/05626 (Plascoat U.K. Limited),based on several phosphorus and nitrogen, compounds among which, inparticular, a combination of melamine phosphate, pentaerythritol andammonium polyphosphate may be mentioned.

In more recent formulations, together with the use of an organic orinorganic phosphorus compound, a nitrogen-containing compound was used,which generally is an aminoplastic resin obtained by condensing urea,melamine or dicyandiamide with formaldehyde.

Examples of double-additive formulations are those reported in U.S. Pat.No. 4,504,610 (Montedison S.p.A.), based on oligomeric derivatives of1,3,5-triazine and ammonium polyphosphate; and EP patent 14,463(Montedison S.p.A.), based on organic compounds selected from amongbenzylguanamine and reaction products of aldehydes with variousnitrogen-containing cyclic compounds, in particularbenzylguanamine/formaldehyde copolymers, and ammonium polyphosphate.

Self-extinguishing compositions can also be obtained by usingsingle-component additives, containing both nitrogen and phosphorus inone single organic molecule, as disclosed in U.S. Pat. No. 4,201,705(Borg-Wagner Corp.).

These intumescent flame-retardant systems endow the polymer whichcontains them, with the property of originating a carbonaceous residueafter a fire or a flame application. This kind or retardant systemsdisplay a number of advantages: absence of phenomena of corrosion in themachines on which the polymers are processed, lower smoke generation ascompared to systems containing metal compounds and halogenatedhydrocarbons, and, above all, the possibility of endowing the polymerswith satisfactory flame-retardant properties with a smaller amount oftotal additive, and, consequently, without an excessive decay of themechanical properties of the same polymers.

The present Applicant has found now that extremely good flame-retardantproperties can be supplied to the above said polymers by means of theuse of a category of simple-structure phosphorus-nitrogen-containingcompounds, based on oligomeric derivatives of2,4,6-triamino-1,3,5-triazine salified with a phosphorus-containingacid.

The novel additives make it also possible, when suitably mixed withammonium and/or amine phosphates and/or phosphonates, polymericcompositions to be obtained which are endowed with excellentself-extinguishing characteristics with a lower total content ofadditives as compared to the prior art, and, therefore, with a furthercontribution to the preservation of chemical and physical properties ofthe polymers in question.

The present Applicant has furthermore evidenced that the reaction ofsalification of oligomeric derivatives of 2,4,6-triamino-1,3,5-triazinewith phosphorus oxy-acids not only makes it possible--as it wasobvious--the amount of ammonium or amine phosphate and/or phosphonate tobe reduced, but also self-extinguishment levels to be reached whichcould not be obtained by simply using the oligomeric triazinicderivatives with ammonium or amine phosphates and/or phosphonates.

The novel additives furthermore display good stability to heat, henceretaining a high activity as flame-retardants also after thehigh-temperature fabrication processes the polymeric compositions whichcontain them are submitted to.

The polymeric compositions containing the phosphorus-nitrogen additivesaccording to the present invention furthermore show the advantage ofgiving rise, in the case of a fire, to a very moderate and non-obscuringsmoke emission.

Therefore, the object of the instant invention are the salts withgeneral formula (I): ##STR2## wherein: R is H or

    --[--C.sub.p H.sub.2p --]--O--R.sub.4

in which

p is an integer comprised within the range of from 2 to 8, andpreferably of from 2 to 4; and

R₄ is H; (C₁ -C₈)-alkyl; preferably H or (C₁ -C₄)-alkyl; (C₂-C₈)-alkenyl; --[--C_(q) H_(2q) --]--O--R₅ in which

q is an integer comprised within the range of from 1 to 4; and

R₅ is H or (C₁ -C₄)-alkyl; (C₆ -C₁₂)-cycloalkyl or alkylcycloalkyl;

R₁ is (C₁ -C₄)-alkyl or R;

or the moiety: ##STR3## is replaced by a heterocyclic radical bonded tothe triazinic ring through the nitrogen atom;

n is an integer comprised within the range of from 2 to 50;

m is a numeral smaller than, or equal to, n; in particular, the ratio ofm/n is comprised within the range of from 0.5 to 1;

Z is a divalent or polyvalent radical falling within the scope of one offollowing formulae: ##STR4## wherein the --R₆ radicals, which may be thesame, or different from each other, are hydrogen or (C₁ -C₄)-alkyl;##STR5## wherein t is an integer comprised within the range of from 2 to14; R₇ is hydrogen, (C₁ -C₄)-alkyl, (C₂ -C₆)-alkenyl, (C₁-C₄)-hydroxyalkyl; ##STR6## wherein s is an integer comprised within therange of from 2 to 5 and w is an integer comprised within the range offrom 1 to 3; ##STR7## wherein: X is a direct --C--C--; O; S; S--S; SO;SO₂ ; NH, NHSO₂ ; NHCO; N=N; CH₂ bond;

R₈ is hydrogen; hydroxy; (C₁ -C₄)-alkyl; (C₁ -C₄)-alkoxy; ##STR8##wherein "A" can be a saturated or unsaturated cycle; ##STR9## wherein shas the above defined meaning; ##STR10## wherein: R₉ is hydrogen or (C₁-C₄)-alkyl;

r is an integer comprised within the range of from 1 to 5;

the indexes s, which are the same, or may be different from each other,have the above defined meaning; ##STR11## wherein: R₉ has the abovedefined meaning;

v is an integer comprised within the range of from 2 to 4;

d is either 1 or 2;

R₂ is H; OH; --O--(C₁ -C₈)-alkyl; --O--(C₆ -C₁₂)-aryl, possiblysubstituted with a (C₁ -C₈)-alkyl; (C₇ -C₁₆)-aralkyl; (C₁ -C₄)-alkylpossibly substituted with a carboxy group; (C₆ -C₁₂)-aryl;

R₃ is H; OH; --O--(C₁ -C₈)-alkyl; --O--(C₆ -C₁₂)-aryl, (C₁ -C₄)-alkyl;(C₆ -C₁₂)-aryl;

R₃ furthermore is: ##STR12## wherein: R₁₀ is hydrogen or (C₁-C₁₂)-alkyl;

Y is OH or R₁₀ ; ##STR13## wherein: R₁₀ has the same meaning as definedhereinabove and R₁₁ radicals, which are the same, or may be differentfrom each other, are hydrogen or (C₁ -C₄)-alkyl;

or the moiety: ##STR14## is replaced by a heterocyclic radical bonded tothe carbon atom through the nitrogen atom and possibly containinganother heteroatom preferably selected from O, S, N; ##STR15## wherein:R₁₂ is hydrogen or (C₁ -C₈)-alkyl; and

w has the same meaning as defined hereinabove; ##STR16## wherein: R₁₃ ishydrogen or hydroxy; ##STR17## wherein: u has the same meaning asdefined above;

or

R₂ and R₃, taken together, may constitute a cyclic structure having theformula: ##STR18##

Examples or R radical, in general formula (I), are:

2-hydroxyethyl; 2-hydroxypropyl; 3-hydroxypropyl; 3-hydroxybutyl;4-hydroxybutyl; 3-hydroxypentyl; 5-hydroxypentyl; 6-hydroxyhexyl;3-hydroxy-2,5-dimethyl-hexyl; 7-hydroxyheptyl; 7-hydroxyoctyl;2-methoxyethyl; 2-methoxypropyl; 3-methoxypropyl; 4-methoxybutyl;6-methoxyhexyl; 7-methoxyheptyl; 7-methoxyoctyl; 2-ethoxyethyl;3-ethoxypropyl; 4-ethoxy-butyl; 3-propoxypropyl; 3-butoxypropyl;4-butoxybutyl; 4-isobutoxybutyl; 5-propoxypentyl; 2-cyclohexyloxy-ethyl;2-ethenyloxyethyl; 2-(2-hydroxyethoxy)-ethyl; 2-(2-methoxyethoxy)-ethyl;and so forth.

Examples of R₁ radical are, besides those as defined for R: methyl;ethyl; propyl; isopropyl; butyl; isobutyl; tert.-butyl.

Examples of heterocyclic radicals which may replace the moiety:##STR19## are: aziridine; pyrrolidine; piperidine; piperazine.

Examples of --Z-- radicals are those deriving, by means of the removalof a hydrogen atom from each reacted amino group, from the followingcompounds: piperazine; 2-methyl-piperazine; 2,5-dimethyl-piperazine;2,3,5,6-tetramethyl-piperazine; 2-ethyl-piperazine;2,5-diethylpiperazine; 1,2-diaminoethane; 1,3-diaminopropane;1,4-diaminobutane; 1,5-diamino-pentane; 1,6-diaminohexane;1,8-diamino-octane; 1,10-diaminodecane; 1,12-diaminododecane;N,N'-dimethyl-1,2-diaminoethane; N-methyl-1,3-diaminopropane;N-ethyl-1,2-diaminoethane; N-isopropyl-1,2-diaminoethane;N-(2-hydroxyethyl)-1,2-diaminoethane;N,N'-bis-(2-hydroxyethyl)-1,2-diaminoethane;N-(2-hydroxyethyl)-1,3-diaminopropane; n-hexenyl-1,6-diaminohexane;N,N'-diethyl-1,4-diamino-2-butene; 2,5-diamino-3-hexene;2-aminoethylether; (2-aminoethoxy)-methyl-ether;1,2-bis-(2-aminoethoxy)-ethane; 1,3-diaminobenzene; 1,4-di-aminobenzene;2,4-diaminotoluene; 2,4-diaminoanisole; 2,4-diaminophenol;4-aminophenylether; 4,4'-methylene-dianiline; 4,4'-diaminobenzanilide;3-aminophenylsulfone; 4-aminophenylsulfone; 4-aminophenylsulfoxide;4-aminophenyldisulfide; 1,3-bis(aminomethyl)benzene;1,4-bis(aminomethyl)benzene; 1,3-bis(aminomethyl)-cyclohexane;1,8-diamino-p-menthane; 1,4-bis(2-aminoethyl)-piperazine;1,4-bis(3-aminopropyl)piperazine; 1,4-bis(4-aminobutyl)piperazine;1,4-bis-(5-aminopentyl)piperazine; bis-(2-aminoethyl)-amine;bis(3-aminopropyl)amine; bis(4-aminobutyl)amine;bis-(5-aminopentyl)amine; bis[2-(N-methylamino)-ethyl]-amine;2-N-butyl-bis-(2-aminoethyl)-amine; bis[3-(N-methylamino)-propyl]-amine;N-(3-aminopropyl)-1,4-di-aminobutane;N-(3-aminopropyl)-1,5-diaminopentane;N-(4-aminobutyl)-1,5-diaminopentane; tris(2-aminoethyl)-amine;tris(3-aminopropyl)-amine; tris(4-aminobutyl)-amine;tris[2-(N-ethylamino)-ethyl]-amine;N,N'-bis(2-aminoethyl)-1,2-diaminoethane;N,N'-bis(3-aminopropyl)-1,3-diaminopropane;N,N'-bis(2-aminoethyl)-1,3-diamino-propane;N,N'-bis(3-aminopropyl)-1,2-diaminoethane;N,N'-bis(3-aminopropyl)-1,4-diaminobutane;bis-[2-(2-aminoethyl)-aminoethyl]-amine;N,N'-bis[2-(2-aminoethyl)-aminoethyl]-1,2-diaminoethane;N,N'-bis[3-(2-aminoethyl)-aminopropyl]-1,2-diaminoethane;N,N,N',N'-tetrakis-(2-aminoethyl)-1,2-diaminoethane; and so forth.

Examples of phosphorus containing acids are: hypophosphorous acid;phosphorous acid; phosphoric acid; pyrophosphoric acid;tripolyphosphoric acid; ethane-1,1,2-triphosphonic acid;2-hydroxyethane-1,1,2-triphosphonic acid; propane-1,2,3-triphosphonicacid; isopropylphosphoric acid; n-butylphosphoric acid;di-n-butylphosphoric acid; di-isopropylphosphoric acid;di-n-pentylphosphoric acid; isooctylphosphoric acid; hexylphosphoricacid; 2-ethylhexylphosphoric acid; methylphosphonic acid;ethylphosphonic acid; n-propylphosphonic acid; n-butylphosphonic acid;amino-methylphosphonic acid; phenylphosphoric acid; phenylphosphonicacid; phenylphosphinic acid; di-n-butylpyrophosphoric acid;di-(2-ethylhexyl)pyro-phosphoric acid; octylphenylphosphoric acid;2-methylbenzylphosphonic acid; 1-aminoethane-1,1-diphosphonic acid;1-hydroxyethane-1,1-diphosphonic acid;1-hydroxydodecane-1,1-diphosphonic acid;1-(N-methylamino)-ethane-1,1-diphosphonic acid;N,N-dimethylaminoethane-1,1-diphosphonic acid;N-butyl-aminomethane-1,1-diphosphonic acid; phosphonoacetic acid;2-phosphonopropionic acid; 3-phosphonopropionic acid; 2-phosphonobutyricacid; 4-phosphonobutyric acid;2-hydroxy-5,5-dimethyl-2-oxo-1,3,2-dioxophosphorinane;3,9-dihydroxy-2,4,8,10-tetraoxo-3,9-diphosphaspiro-[5,5]-undecane-3,9-dioxide;amino-tris(methylenephosphonic) acid;ethylenediaminotetra(methylenephosphonic) acid;hexamethylenediaminotetra(methylenephosphonic) acid;diethylenetriaminopenta(methylenephosphonic) acid; and so forth.

Specific compounds falling within the scope of formula (I) are reportedin the Examples which follow the instant disclosure.

The products of general formula (I) can be synthetized by reacting--inthe presence of a suitable solvent (such as, e.g., water, methylalcohol, ethyl alcohol, acetonitrile,) at temperatures comprised withinthe range of from 0° C. to the boiling point of the solvent used--anoligomeric derivative of 2,4,6-triamino-1,3,5-triazine, having thegeneral formula (XIV): ##STR20## wherein R, R₁, Z and n have the samemeaning as defined hereinabove, with a phosphorus-containing acid havingthe general formula (XV): ##STR21## wherein R₂ and R₃ have the samemeaning as defined hereinabove, or, if the phosphorus-containing acidmay act as a solvent, in the absence of solvents and with an excess ofphosphorus-containing acid, at temperatures comprised within the rangeof from 0° to 150° C.

The resulting salt product can be easily separated from the reactionmass by filtration, or by distilling off the solvent.

In general, products of general formula (I) are obtained as crystallinepowders of white colour, which are of good quality and can be used inself-extinguishing composition without any further purification steps.

Some of the intermediates of general formula (XIV) are known; however,they can be easily synthetized according to the general methodschematically shown hereinunder: ##STR22## or according to as disclosedin Italian patent application No. 21 456 A/90 filed by the presentApplicant on Sep. 13th, 1990.

Also the phosphorus-containing acids having the general formula (XV) areknown, and many of them are also available in commercial amounts.

Another object of the present invention are the self-extinguishingpolymeric compositions comprising:

(a) from 90 to 40 parts by weight of a thermoplastic polymer, or of apolymer endowed with elastomeric properties;

(b) from 7 to 28, preferably from 8 to 25, parts by weight of one ormore ammonium or amine phosphate(s) or phosphonate(s);

(c) from 3 to 32, preferably from 4 to 25, parts by weight of one ormore oligomeric derivative(s) of 2,4,6-triamino-1,3,5-triazine salifiedwith a phosphorus oxyacid, said oligomeric derivatives of2,4,6-triamino-1,3,5-triazine having the general formula (XIV):##STR23## wherein R, R₁, Z and n have the same meaning as definedhereinabove.

The (c) component is preferably selected from the salts having thegeneral formula (I): ##STR24## wherein the radicals from R to R₃, Z, nand m have the same meaning as defined hereinabove.

Particularly preferred are the salts of those compounds of generalformula (XIV), wherein the R radical is replaced by a

    --[--C.sub.p H.sub.2p --]--O--R.sub.4

moiety, in which p is an integer comprised within the range of from 2 to4 and R₄ is hydrogen or (C₁ -C₄)-alkyl; or R₁ radical is hydrogen, orthe moiety: ##STR25## is replaced by an --NH₂ radical or a heterocyclicradical selected from among aziridine, pyrrolidine, piperidine,piperazine.

Among the phosphates, those ammonium polyphosphates are preferred whichfall within the scope of the general formula

    (NH.sub.4).sub.n+2 P.sub.n O.sub.3n+1

in which n represents and integer equal to, or larger than, 2;preferably, the molecular weight of polyphosphates should be highenough, in order to secure a low solubility in water. For indicativepurposes, n is preferably comprised within the range of from 2 to 500.

The composition of the polyphosphates having the formula indicatedhereinabove, in which n is a large enough numeral and is preferablycomprised within the range of from 50 to 500, practically is thecomposition which corresponds to the formula of metaphosphates

    (NH.sub.4 PO.sub.3).sub.n.

An example for such polyphosphates is the product known under the tradename "Exolit 422" (manufactured and marketed by Hoechst) and having thecomposition (NH₄ PO₃)_(n), in which n is larger than 50; another exampleis the product known under the trade name "Phos-Chek P/30" (MonsantoChemical) and having an analogous composition.

Another polyphosphate which may be advantageously used, above all thanksto its low solubility in water, is the product known under the tradename "Exolit 462" (manufactured and marketed by Hoechst) andcorresponding to Exolit 422 microencapsulated in melamine-formaldehyderesin.

Other phosphates which can be used are those deriving from amines, suchas, e.g., dimethylammonium or diethylammonium phosphate, ethylenediaminephosphate, melamine ortho- or pyrophosphate.

Among phosphonates, extremely good results were obtained by using those(mono- or poly-substituted) ammonium phosphonates which are derived frommono- and poly-phosphonic acids, examples of which are:ethane-1,1,2-triphosphonic acid; 2-hydroxyethane-1,1,2-triphosphonicacid; propane-1,2,3-triphosphonic acid; methyl-phosphonic acid;ethyl-phosphonic acid; n-propylphosphonic acid; n-butylphosphonic acid;phenylphosphonic acid; 1-amino-ethane-1,1-diphosphonic acid;1-hydroxyethane-1,1-diphosphonic acid;1-hydroxydodecane-1,1-diphosphonic acid; phosphonoacetic acid;2-phospho-nopropionic acid; 3-phosphonopropionic acid;2-phospho-nobutyric acid; 4-phosphonobutyric acid;amino-tris(methylenephosphonic) acid;ethylenediaminotetra(methylenephosphonic) acid;hexamethylenediaminotetra(methylenephosphonic) acid;diethylenetriaminopenta(methylenephosphonic) acid; and so forth.

Among the polymers which can be used in the compositions according tothe present invention, those polymers and copolymers of olefines arepreferred which have the general formula

    R--CH═CH.sub.2

in which R is a hydrogen atom, or a C₁ -C₈ alkyl or aryl radical; inparticular:

1. isotactic or prevailingly isotactic polypropylene;

2. HDPE, LLDPE, LDPE polyethylene;

3. crystalline propylene copolymers containing minor proportions ofethylene and/or other alpha-olefins, such as, e.g., 1-butene, 1-hexene,1-octene, 4-methyl-1-pentene;

4. heterophasic compositions comprising

(A) a fraction consisting of a propylene copolymer, or of one of thecopolymers according to (3); and

(B) a copolymeric fraction formed by elastomeric copolymers of ethylenewith an alpha-olefin, possibly containing minor proportions of a diene,with said alpha-olefin being preferably selected from propylene and1-butene;

5. elastomeric copolymers of ethylene with alpha-olefins possiblycontaining minor proportions of a diene.

Examples of dienes which are more commonly used in said elastomericcopolymers are butadiene, ethylidene-norbornene, hexadiene-1,4.

Among the polymers of olefins with formula

    R--CH═CH.sub.2

in which R is an aryl radical, "Crystal" and impact resistantpolystyrene are preferred.

Other examples of polymers which can be commonly used areacrylonitrile/butadiene/styrene (ABS) and styrene/acrylonitrile (SAN)copolymers; (polyester and polyether) polyurethane; poly-(ethyleneterephthalate); poly-(butylene terephthalate) and polyamides.

The self-extinguishing compositions according to the present inventioncan be prepared by means of methods known from the prior art: forexample, ammonium or amine phosphate or phosphonate is first intimatelymixed with one or more salts of the compounds of general formula (XIV)in finely subdivided form (with their particles being preferably smallerthan 70 micrometers) and the resulting mixture is added to the polymerin a turbomixer, in order to produce a homogeneous blend which issubsequently extruded and pelletized. The granular product obtained inthat way can be transformed into various articles of manufacture bymeans of any of the well-known, available moulding techniques.

The flame-retardant additives according to the present invention arealso suitable for use in the field of flame-retardant paints.

Oligomeric compounds with salt character falling within the scope ofgeneral formula (I) not cited in the examples, but equallyadvantageously useable in the self-extinguishing polymeric compositionsaccording to the present invention, are those reported in followingTable 1.

                                      TABLE 1                                     __________________________________________________________________________     poundsCom-                                                                        ##STR26##         Z                      n                                                                               nm/                                                                             ##STR27##                   __________________________________________________________________________     1  CH.sub.2 CH.sub.2 OH                                                                     CH.sub.2 CH.sub.2 OH                                                                  ##STR28##             14                                                                              0.7                                                                             H.sub.3 PO.sub.3              2  CH.sub.2 CH.sub.2 OH                                                                     CH.sub.3                                                                              ##STR29##             15                                                                              1 H.sub.3 PO.sub.4              3  CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                       H                                                                                     ##STR30##             13                                                                              1 H.sub.3 PO.sub.4              4  (CH.sub.2).sub.5 OH                                                                      H                                                                                     ##STR31##             18                                                                              0.6                                                                              ##STR32##                    5  CH.sub.2 CH.sub.2 OCH.sub.3                                                              H      N(CH.sub.2 CH.sub.2NH).sub.3                                                                         12                                                                              1 H.sub.3 PO.sub.4              6                                                                                 ##STR33## H                                                                                     ##STR34##             21                                                                              0.4                                                                              ##STR35##                    7  CH.sub.2 CH.sub.2 OCHCH.sub.2                                                            H                                                                                     ##STR36##             20                                                                              1 H.sub.3 PO.sub.4              8  H          H                                                                                     ##STR37##             15                                                                              0.7                                                                              ##STR38##                    9  (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OCH.sub.3                                             H                                                                                     ##STR39##             14                                                                              1 H.sub.3 PO.sub.4             10  H          H      HNCH.sub.2 CH.sub.2 NH 17                                                                              0.5                                                                              ##STR40##                                                                     ##STR41##                   11  CH.sub.2 CH.sub.2 OCH.sub.3                                                              H                                                                                     ##STR42##             18                                                                              1 H.sub.3 PO.sub.3             12                                                                                 ##STR43## H                                                                                     ##STR44##             15                                                                              0.8                                                                             H.sub.3 PO.sub.4             13  CH.sub.2 CH.sub.2 OCH.sub.3                                                              H      HN(CH.sub.2).sub.2 N(CH.sub.2).sub.2 N(CH.sub.2).sub                          .2 NH                  11                                                                              0.5                                                                             H.sub.3 PO.sub.4             14  H          H                                                                                     ##STR45##             16                                                                              1 H.sub.3 PO.sub.4             15  CH.sub.2 CH.sub.2 OH                                                                     H      HN(CH.sub.2).sub.2 O(CH.sub.2).sub.2 NH                                                              15                                                                              1 H.sub.3 PO.sub.4             16  (CH.sub.2).sub.3 OCH.sub.3                                                               H                                                                                     ##STR46##             16                                                                              0.7                                                                             H.sub.3 PO.sub.4             17  CH.sub.2 CH.sub.2 OCH.sub.3                                                              H                                                                                     ##STR47##             17                                                                              1 H.sub.3 PO.sub.3             18  H          H                                                                                     ##STR48##             14                                                                              0.3                                                                              ##STR49##                   19  (CH.sub.2).sub.4 OCH.sub.3                                                               H                                                                                     ##STR50##             18                                                                              1 H.sub.3 PO.sub.4             20  (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                    H      HNCH.sub.2 CH.sub.2 NH 15                                                                              0.8                                                                             H.sub.3 PO.sub.3             21  CH.sub.2 CH.sub.2 OH                                                                     CH.sub.3                                                                              ##STR51##             20                                                                              1 H.sub.3 PO.sub.4             22  CH.sub.2 CH.sub.2 OCH.sub.3                                                              H                                                                                     ##STR52##             19                                                                              1 H.sub.3 PO.sub.4             23  (CH.sub.2).sub.3 OH                                                                      H                                                                                     ##STR53##             16                                                                              0.6                                                                             H.sub.3 PO.sub.4             24  CH.sub.2 CH.sub.2 OH                                                                     H                                                                                     ##STR54##             14                                                                              0.4                                                                              ##STR55##                   __________________________________________________________________________

The following examples illustrate the features of the present invention,without limiting them.

The salifying reaction between the intermediates with general formula(XIV) and the phosphorus-containing acids with general formula (XV) areconfirmed by I.R. spectroscopic analysis carried out on the I.R.spectrophotometer Model Perkin Elmer 580 B with raster.

In fact, it was observed that an extremely good reference signal isconstituted by the band relevant to the off-plane deformation of thetriazinic ring: said band is at approximately 830-800 cm⁻¹ in the caseof the not perturbed ring, and is at 795-760 cm⁻¹ in the case of thering with salified amino groups.

EXAMPLE 1

184.5 g of cyanuric chloride and 700 cm³ of water are added to a reactorof 2 liters of capacity, equipped with stirrer, thermomemter, additionfunnel, reflux condenser and cooling bath.

With cooling from the outside, 75 g of 2-methoxyethylamine and 40 g ofsodium hydroxide dissolved in 150 cm³ of water are simultaneously addedduring a 3-hours time, with pH being kept at a value comprised withinthe range of from 5 to 7 and temperature being comprised within therange of from 0° to 3° C.

The reaction mixture is kept at the temperature of 0°-3° C. for afurther 2 hours, then the resulting product is filtered off and iswashed on the filter with water.

By drying the filter cake inside an oven at 50° C., under vacuum, 214.5g of intermediate (XVI): ##STR56## is obtained as a white crystal powderwith melting point (m.p.)=73°-75° C., and with a chlorine content of31.68% (theoretical value: 31.84%).

The structure of the intermediate was furthermore confirmed by N.M.R.analysis.

To the same reaction vessel of 2 liters of capacity, but equipped withheating bath, 800 cm³ of xylene, 50 cm³ of water and 100 g ofintermediate (XVI) and then, with stirring, and during 20 minutes, 26.9g of ethylenediamine, are added.

The temperature of the dispersion increases up to 60°-65° C.; it isadjusted at 75° C. by means of the external heating bath, and is stirredat that temperature for about 1 hour.

Then, 17.5 g of sodium hydroxide dissolved in 40 cm³ of water is addedduring a 2-hours time, and at the temperature of 75° C.

The temperature is increased up to 95° C. and the reaction mixture iskept stirred at that temperature for about 2 hours.

Then, 18.4 of sodium hydroxide dissolved in 40 cm³ of water is addedduring about 2 hours.

The temperature is gradually increased with water being removed byazeotropic distillation, until the boiling temperature of the solvent isreached.

The reaction mixture is kept refluxing for 10 hours, then the resultingmass is cooled down to room temperature, and the resulting product isfiltered.

The filter cake is thoroughly pressed and is washed with plentifulwater.

After oven drying at 100° C., 84.9 of intermediate (XVII): ##STR57## isobtained as a crystalline powder of white colour, with m.p. =182°-186°C. and with n=20.

500 cm³ of acetonitrile, 63.0 g of intermediate (XVII) and, withstirring, 36.3 g of phosphoric acid at 85% by weight are added to a1-liter reactor equipped with stirrer, thermomemter, addition funnel,reflux condenser and heating bath.

The resulting reaction mixture is heated up to boiling, and is keptrefluxing for 12 hours.

After cooling down to room temperature, the resulting product isfiltered off and the filter cake is washed on the filter withacetonitrile.

After oven-drying the filter cake at 100° C., 89.1 g of the product:##STR58## is obtained as a crystalline powder of white colour with m.p.=165°-170° C., with n=20 and m/n=1, and with a phosphorus content of9.82% (theoretical value: 10.06%).

EXAMPLE 2

To the same reactor of Example 1, 800 cm³ of water and 184.5 g ofcyanuric chloride are added.

By following the same procedure as disclosed in Example 1, 133 g ofbis(2-methoxyethylamine) is added.

By continuing to operate according to the modalities shown in saidExample, 260.8 g of intermediate (XVIII): ##STR59## is obtained as awhite crystal powder with m.p. =62°-65° C., and with a chlorine contentof 25.08% (theoretical value: 25.27%).

The structure of the intermediate (XVIII) was furthermore confirmed byN.M.R. analysis.

To the same reaction vessel of 2 liters of capacity as of Example 1, 800cm³ of xylene, 50 cm³ of water and 135 g of intermediate (XVIII) andthen, with stirring, and during 15 minutes, 41.3 g of piperazine areadded.

The temperature of the suspension increases up to 40°-45° C.

Then, still following the same operating modalities as disclosed inExample 1 (in this case, 38 g of sodium hydroxide is used), 136.4 ofintermediate (XIX): ##STR60## is obtained as a crystalline powder ofwhite colour, with m.p. >300° C. and with n=18.

600 cm³ of acetonitrile, 88.2 g of intermediate (XIX) and, withstirring, 25.8 g of phosphorous acid are added to the same 1-literreactor as of Example 1.

The resulting reaction mixture is heated up to its boiling temperature,and is kept refluxing for 12 hours.

After cooling down to room temperature, the resulting product isfiltered off and the filter cake is washed on the filter withacetonitrile.

After oven-drying the filter cake at 100° C., 109.7 g of product:##STR61## is obtained as a crystalline powder of white colour withm.p.=283°-287° C., with n=18 and m/n=1, and with a phosphorus content of8.01% (theoretical value: 8.24%).

EXAMPLE 3

400 cm³ of acetone and 100 g of cyanuric chloride are added to the same2-liter reactor as of Example 1.

The suspension is cooled down to 0°-5° C. and 23.4 g of piperazine isthen added, during a 1-hour time.

Still at 0°-5° C., and during a 2-hour time, 23.3 g of piperazine and10.8 g of sodium hydroxide dissolved in 50 cm³ of water are fedsimultaneously, in such a way as to keep pH at a value of round 3.

The temperature is increased up to 20° C. during about 2 hours and 10.8g of sodium hydroxide dissolved in 50 cm³ of water are simultaneouslyadded, so as to keep pH at a value of round 5.

The temperature is further gradually increased from to 20°to 60° C.,with a solution consisting of 21.8 g of sodium hydroxide in 100 cm³ ofwater being simultaneously fed.

The reaction mass is kept stirred at 60° C. for a further 2 hours, andthen is cooled down to room temperature, and the resulting product isfiltered off, and is washed on the filter, with water.

By drying the filter cake in an oven at 100° C., 104.9 g of intermediate(XX): ##STR62## is obtained as a crystalline powder of white colour,with m.p.>300° C. and with n=15, and with a chlorine content of 17.70%(theoretical value: 17.94%).

The structure of the intermediate was furthermore confirmed by I.R.spectroscopic analysis.

400 cm³ of water, 125 g of a solution of ammonium hydroxide at 30% byweight and 100 of intermediate (XX) are added to a steel reactor of 1liter of capacity.

The reaction mixture is then heated to 150° C. and is kept at thattemperature for 12 hours.

The reaction mixture is cooled down to room temperature, the resultingproduct is filtered off and the filter cake is washed on the filter,with water.

By oven-drying the filter cake in the oven at 100° C., 87.1 ofintermediate (XXI): ##STR63## is obtained as a crystalline powder ofwhite colour, with m.p.>300° C. and with n=15.

600 cm³ of acetonitrile, 53.4 g of intermediate (XXI) and, withstirring, 36.3 of phosphoric acid at 85% by weight are charged to a1-liter reactor, equipped as in the preceding Examples.

The reaction mass is heated up to boiling temperature, and is keptrefluxing for 14 hours.

Then, by proceeding analogously to as disclosed in Example 1, 82.1 g ofproduct: ##STR64## is obtained as a crystalline powder of white colourwith m.p.>300° C., with n=15 and m/n=1, and with a phosphorus content of11.06% (theoretical value: 11.23%).

EXAMPLE 4

To a 2-liter reactor equipped as in Example 1, 800 cm³ of xylene, 100 gof intermediate (XVI), 38.6 g of piperazine and 35.9 g of sodiumhydroxide are added.

The reaction mass is heated up to its boiling temperature, and is keptrefluxing for 24 hours.

At the end, the reaction mixture is cooled down to room temperature, theresulting product is filtered off and the filter cake is washed on thefilter with plentiful water.

By drying the filter cake 100.8 g of intermediate (XXII): ##STR65## isobtained as a crystalline powder of white colour with m.p.>300° C., andwith n=16.

500 cm³ of acetonitrile, 59 g of intermediate (XXII) and, with stirring,30.2 of phosphoric acid at 85% by weight are charged to a 1-literreactor, equipped as in the preceding Example 1.

The reaction mass is heated up to boiling temperature, and is keptrefluxing for 14 hours.

Then, by proceeding analogously to as disclosed in Example 1, 82.4 g ofproduct: ##STR66## is obtained as a crystalline powder of white colourwith m.p.>300° C., with n=16 and m/n=1, and with a phosphorus content of9.41% (theoretical value: 9.28%).

EXAMPLE 5

To a 1-liter reactor equipped as in Example 1, 328 g of phosphorous acidand 82 g of acetonitrile are added. The reaction mixture is graduallyheated up to 160° C. in 6 hours.

A crystalline product of white colour is formed.

The reaction mixture is subsequently cooled down to 80° C., 500 cm³ ofwater is then added to the reaction mixture with good stirring, then thereaction mixture is allowed to cool down to room temperature.

The resulting product is filtered off and the filter cake is washed onthe filter with a little of water.

By drying the filter cake 290 g of 1-aminoethane-1,1-diphosphonic acidis obtained as a crystalline powder of white colour with m.p.=265°-270°C. (with decomposition), and with a phosphorus content of 29.4%(theoretical value: 30.24%).

600 cm³ of water and 71.2 g of intermediate (XXI) are charged to thesame 1-liter reactor.

The reaction mass is heated up to 80° C. and 41.0 g of1-aminoethane-1,1-diphosphonic acid is added with stirring.

The reaction mixture is heated up to boiling, and is kept approximately8 hours under refluxing conditions.

The reaction mixture is then cooled down to room temperature, theresulting product is filtered off and the filter cake is washed on thefilter, with water.

After drying the filter cake, 112.2 g of product: ##STR67## is obtainedas a crystalline powder of white colour with m.p.>300° C., with n=15 andm/n=0.5, and with a phosphorus content of 10.87% (theoretical value:11.05%).

EXAMPLE 6

To a 1-liter reactor equipped as in Example 1, 350 cm³ of xylene, 30 cm³of water, 66.9 g of intermediate (XVI), and, with stirring and duringabout 15 minutes, 30.9 g of diethylenetriamine are added.

Then, by subsequently proceeding according to the same operatingmodalities as disclosed in Example 1 (in this case, 24 g of sodiumhydroxide is used), 72.8 g of intermediate (XXIII): ##STR68## isobtained as a crystalline powder of white colour with m.p.>300° C., andwith n=18.

600 cm³ of water, 75.9 g of intermediate (XXIII) and, with stirring andduring 15 minutes, 61.8 g of a solution at 60% by weight of1-hydroxyethane-1,1-diphosphonic acid are added to the same 1-literreactor.

The reaction mass is heated up to boiling temperature, and is keptrefluxing for 12 hours.

The reaction mass is cooled down to room temperature, the resultingproduct is filtered off and the filter cake is washed on the filter,with water.

By oven-drying the filter panel at 100° C., 111.8 g of product:##STR69## is obtained as a crystalline powder of white colour withm.p.>300° C., with n=18 and m/n=0.6, and with a phosphorus content of9.64% (theoretical value: 9.88%).

EXAMPLES 7-15

By operating under analogous conditions to as disclosed in Examples 1-6,the products with general formula (I) are prepared, which are reportedin following Table 2.

                                      TABLE 2                                     __________________________________________________________________________     N.ampleEx-                                                                        ##STR70##    Z              n                                                                               nm/                                                                             ##STR71##   (°C.)pointMelting                                                           ComputedFoundcontent                                                         , %Phosphorus            __________________________________________________________________________     7  CH.sub.2 CH.sub.2 OH                                                                    H                                                                                 ##STR72##     20                                                                              1 H.sub.3 PO.sub.4                                                                          >300  9.69  9.42               8  CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                    H                                                                                 ##STR73##     22                                                                              1 H.sub.3 PO.sub.4                                                                          218-224                                                                             8.91  8.78               9  H         H                                                                                 ##STR74##     15                                                                              0.5                                                                             H.sub.3 PO.sub.4                                                                          >300  6.83  6.67              10  H         H                                                                                 ##STR75##     15                                                                              1                                                                                ##STR76##  >300  9.23  9.02              11  CH.sub.2 CH.sub.2 OH                                                                    CH.sub.3                                                                         HN(CH.sub.2).sub.6 NH                                                                        21                                                                              1 H.sub.3 PO.sub.4                                                                          >300  8.52  8.68              12  CH.sub.2 CH.sub.2 OCH.sub.3                                                             H                                                                                 ##STR77##     18                                                                              1 H.sub.3 PO.sub.3                                                                          >300  7.56  7.41              13  CH.sub.2 CH.sub.2 OCH.sub.3                                                             H                                                                                 ##STR78##     16                                                                              1 H.sub.3 PO.sub.4                                                                          >300  8.71  8.47              14  H         H  HNCH.sub.2 CH.sub.2 NH                                                                       17                                                                              0.4                                                                              ##STR79##  >300 11.11 10.96              15  H         H                                                                                 ##STR80##     15                                                                              0.5                                                                              ##STR81##  >300 11.03 11.27              16  tert.-C.sub.4 H.sub.9                                                                   H                                                                                 ##STR82##     24                                                                              1 H.sub.3 PO.sub.4                                                                          >300  9.33  9.48              17                                                                                 ##STR83##                                                                                  ##STR84##     18                                                                              1 H.sub.3 PO.sub.4                                                                          >300  9.39  9.21              __________________________________________________________________________

TABLES 3 and 4

The tests reported in these tables relate to polymeric compositionscontaining the products of general formula (I) prepared according to thepreceding examples.

Specimens consisting of approximately 3 mm thick slabs were prepared bymoulding blends of granular polymers and additives, on a MOORE platenpress, with a moulding time of 7 minutes under a pressure of 40 kg/cm².

On the resulting slabs, the self-extinguishment level was determined bymeasuring the oxygen index (L.O.I. according to ASTM D-2863/77) on aStanton RedCroft instrument and applying the "Vertical Burning Test",which makes it possible the material to be classified at three levels(94 V-0, 94 V-1, 94 V-2, according to UL 94 standard procedures (issuedby Underwriters Laboratories--U.S.A.).

In Table 3, the values are reported which were obtained by using anisotactic polypropylene in flake form having a Melt Flow Index of 12 anda content of insolubles in boiling n-heptane of 96% by weight.

In Table 4 the values are reported which were obtained by usinglow-density polyethylene pellets having a Melt Flow Index of 7;polystyrene pellets containing 5% by weight of butadiene rubber andhaving a Melt Flow Index of 9; thermoplastic polyurethane pellets ofboth polyester (ESTANE 54600.sup.(R) ex Goodrich) and polyether type(ESTANE 58300.sup.(R) ex Goodrich), with specific weights of 1.19 and1.10 g/cm³ respectively; an elastomeric ethylene-propylene copolymerwith a % propylene content of 45; an acrylonitrile-butadiene-styreneterpolymer having a specific gravity of 1.06 g/cm³, a Melt Flow Index of1.6 and containing about 40% of acrylonitrile and styrene and 20% ofbutadiene.

                                      TABLE 3                                     __________________________________________________________________________         Product                                                                  Example                                                                            of Example                                                                          Parts by weight  L.O.I.   UL 94                                    N.   N.    Product                                                                            PP.sup.[1]                                                                       AO.sup.[2]                                                                        APP.sup.[1]                                                                        (ASTM D 2863)                                                                          3 mm                                     __________________________________________________________________________    18   1     11.0 77 1   11.0 32.2     V0                                       19   2     12.0 75 1   12.0 32.0     V0                                       20   3     5.4  80 1   13.6 35.0     V0                                       21   3     19.5 70 1   9.5  33.3     V0                                       22   4     4.0  83 1   12.0 30.0     V2                                       23   4     6.3  80 1   12.7 35.5     V0                                       24   5     6.3  80 1   12.7 34.0     V0                                       25   6     5.4  80 1   13.6 34.8     V0                                       26   7     6.3  80 1   12.7 34.9     V0                                       27   8     8.0  75 1   16.0 37.4     V0                                       28   9     8.0  75 1   16.0 34.7     V0                                       29   10    12.0 75 1   12.0 31.7     V0                                       30   11    9.5  80 1   9.5  32.1     V1                                       31   12    6.3  80 1   12.7 33.0     V0                                       32   13    7.0  78 1   14.0 30.8     V1                                       33   14    6.3  80 1   12.7 32.4     V0                                       34   15    4.6  83 1   11.4 29.8     V2                                       35   15    6.3  80 1   12.7 34.8     V0                                       36   16    12.0 75 1   12.0 34.4     V0                                       37   17    12.0 75 1   12.0 36.0     V0                                       38   15    8.0  75 1   *16.0                                                                              37.9     V0                                       39   4     12.0 75 1   .sup.[3] 12.0                                                                      35.8     V0                                       __________________________________________________________________________     .sup.[1] PP = polypropylene                                                   APP = ammonium polyphosphate  Exolit 422 .sup.(®) (Hoechst)               * = APP microencapsulated with Exolit 462 .sup.(®)                        melamineformaldehyde resin (Hoechst)                                          .sup.[2] AO = Antioxidant                                                     A mixture constituted by 2 parts of dilaurylthiopropionate and 1 part of      pentaerythritol tetra[3-(3,5-di-tert.                                         .sup.[3]  = APP was replaced by monoammonium salt of                          1aminoethane-1,1-diphosphonic acid.                                      

                                      TABLE 4                                     __________________________________________________________________________               Product                                                            Example                                                                            Polymeric                                                                           of Example                                                                          Parts by weight   L.O.I.   UL 94                             N.   support                                                                             N.    Product                                                                            Polymer                                                                            AO.sup.[2]                                                                        APP.sup.[1]                                                                       (ASTM D 2863)                                                                          3 mm                              __________________________________________________________________________    40   LDPE  1     7.3  70   1   21.7                                                                              33.7     V0                                41         3     6.4  70   1   22.5                                                                              32.0     V0                                42         4     5.3  75   1   18.7                                                                              32.1     V0                                43         15    14.5 70   1   14.5                                                                              33.2     V0                                44   HIPS  3     8.5  65   1   25.5                                                                              32.7     V0                                45         10    7.3  70   1   21.7                                                                              31.4     V0                                46   PU    3     16.0 75   1   8.0 34.2     V0                                47   (ester)                                                                             5     16.0 75   1   8.0 33.4     V0                                48   PU    5     19.4 70   1   9.7 31.4     V0                                     (ether)                                                                  49   PP/PE 4     12.0 75   1   12.0                                                                              34.0     V0                                50   ABS   10    7.0  71   1   21.0                                                                              30.8     V0                                __________________________________________________________________________     .sup.[1] APP = ammonium polyphosphate  Exolit 422 .sup.(®) (Hoechst)      .sup.[2] LDPE = Lowdensity polyethylene                                       HIPS = polystyrene containing 5% of butadiene rubber                          (ester) PU = Polyester polyurethane                                           (ether) PU = Polyether polyurethane                                           PP/PE = propyleneethylene copolymer                                           ABS = acrylonitrilebutadiene-styrene terpolymer                               .sup.[3] AO = Antioxidant                                                     A mixture constituted by 2 parts of dilaurylthiopropionate and 1 part of      pentaerythritol tetra[3-(3,5-di-tert. butyl4-hydroxyphenyl)-propionate]- 

We claim:
 1. Salts of triazinic compounds with phosphorus oxyacids,having the general formula (I): ##STR85## wherein: R is H or

    --[--C.sub.p H.sub.2p --]--O--R.sub.4

in which p is an integer comprised within the range of from 2 to 8; andR₄ is H; (C₁ -C₈)-alkyl; (C₂ -C₈)-alkenyl; --[--C_(q) H_(2q) --]--O--R₅,in which q is an integer comprised within the range of from 1 to 4; andR₅ is H or (C₁ -C₄)-alkyl; (C₆ -C₁₂)-cycloalkyl or alkylcycloalkyl; R₁is (C₁ -C₄)-alkyl or R; or the moiety: ##STR86## is replaced by aheterocyclic radical bonded to the triazinic ring through the nitrogenatom; wherein said heterocyclic radical is selected from the groupconsisting of aziridine, pyrrolidine, piperidine, and piperazineradicals; n is an integer comprised within the range of from 2 to 50; mis a numeral smaller than, or equal to, n; z is a divalent or polyvalentradical falling within the scope of one of following formulae: ##STR87##wherein the --R₆ radicals, which may be the same, or different from eachother, are hydrogen or (C₁ -C₄)-alkyl; ##STR88## wherein t is an integercomprised within the range of from 2 to 14; R₇ is hydrogen, (C₁-C₄)-alkyl, (C₂ -C₆)-alkenyl, (C₁ -C₄)-hydroxyalkyl; ##STR89## wherein sis an integer comprised within the range of from 2 to 5 and w is aninteger comprised within the range of from 1 to 3; ##STR90## wherein: Xis a direct --C--C--; O; S; S--S; SO; SO₂ ; NH; NHSO₂ ; NHCO; N=N; CH₂bond; R₈ is hydrogen; hydroxy; (C₁ -C₄)-alkyl; (C₁ -C₄)-alkoxy;##STR91## wherein "A" can be a saturated or unsaturated cycle; ##STR92##wherein s has the above defined meaning; ##STR93## wherein; R₉ ishydrogen or (C₁ -C₄)-alkyl;r is an integer comprised within the range offrom 1 to 5; the indexes s, which are the same, or may be different fromeach other, have the above defined meaning; ##STR94## wherein: R₉ hasthe above defined meaning; v is an integer comprised within the range offrom 2 to 4; d is either 1 or 2; R₂ is H; OH; --O--(C₁ -C₈)-alkyl;--O--(C₆ -C₁₂)-aryl, possibly substituted with a (C₁ -C₈)-alkyl; (C₇-C₁₆)-aralkyl; (C₁ -C₄)-alkyl possibly substituted with a carboxy group;(C₆ -C₁₂)-aryl; R₃ is H; OH; --O--(C₁ -C₈)-alkyl; --O--(C₆ -C₁₂)-aryl,(C₁ -C₄)-alkyl; (C₆ -C₁₂)-aryl; R₃ furthermore is: ##STR95## wherein:R₁₀ is hydrogen or (C₁ -C₁₂)-alkyl;Y is OH or R₁₀ ; ##STR96## wherein:R₁₀ has the same meaning as defined hereinabove and R₁₁ radicals, whichare the same, or may be different from each other, are hydrogen or (C₁-C₄)-alkyl; or the moiety: ##STR97## is replaced by a heterocyclicradical bonded to the carbon atom through the nitrogen atom wherein saidheterocyclic radical is selected from the group consisting of azirdine,pyrrolidine, piperidine, or piperazine radicals; ##STR98## wherein: R₁₂is hydrogen or (C₁ -C₈)-alkyl; and w has the same meaning as definedhereinabove; ##STR99## wherein: R₁₃ is hydrogen or hydroxy; ##STR100##wherein: u has the same meaning as defined above; or R₂ and R₃, takentogether, may constitute a cyclic structure having the formula:##STR101##
 2. Salts of triazinic compounds with phosphorus oxyacidsaccording to claim 1, in which said phosphorus acid is selected from:hypophosphorous acid; phosphorous acid; phosphoric acid; pyrophosphoricacid; tripolyphosphoric acid; ethane-1,1,2-triphosphonic acid;2-hydroxyethane-1,1,2-triphosphonic acid; propane-1,2,3-triphosphonicacid; isopropylphosphoric acid; n-butylphosphoric acid;di-n-butylphosphoric acid; di-isopropylphosphoric acid;di-n-pentylphosphoric acid; isooctylphosphoric acid; hexylphosphoricacid; 2-ethylhexylphosphoric acid; methylphosphonic acid;ethylphosphonic acid; n-propylphosphonic acid; n-butylphosphonic acid;aminomethylphosphonic acid; phenylphosphoric acid; phenylphosphonicacid; phenylphosphinic acid; di-n-butylpyrophosphoric acid;di-(2-ethylhexyl)pyrophosphoric acid; octylphenylphosphoric acid;2-methylbenzylphosphonic acid; 1-aminoethane-1,1-diphosphonic acid;1-hydroxyethane-1,1-diphosphonic acid;1-hydroxydodecane-1,1-diphosphonic acid;1-(N-methylamino)-ethane-1,1-diphosphonic acid;N,N-dimethylaminoethane-1,1-diphosphonic acid;N-butyl-aminomethane-1,1-diphosphonic acid; phosphonoacetic acid;2-phosphonopropionic acid; 3-phosphonopropionic acid; 2-phosphonobutyricacid; 4-phosphonobutyric acid;2-hydroxy-5,5-dimethyl-2-oxo-1,3,2-dioxophosphorinane;3,9-dihydroxy-2,4,8,10-tetraoxo-3,9-diphosphaspiro-[5,5]-undecane-3,9-dioxido;amino-tris(methylenephosphonic) acid;ethylenediaminotetra(methylene-phosphonic) acid;hexamethylenediaminotetra(methylene-phosphonic) acid;diethylenetriaminopenta(methylenephosphonic) acid; and so forth.